# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2014

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#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
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#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
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data_2

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
'(S)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid'
_chemical_formula_moiety         'C12 H16 N O4 1+, Cl 1-, C H4 O'
_chemical_formula_sum            'C13 H20 Cl N O5'
_chemical_compound_source        synthesis
_exptl_crystal_recrystallization_method methanol
_chemical_melting_point          511

_exptl_crystal_description       block
_exptl_crystal_colour            colorless

_diffrn_ambient_temperature      296(2)
_chemical_formula_weight         305.75

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P 21 21 21'
_symmetry_int_tables_number      19
_chemical_absolute_configuration ad

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   6.2745(4)
_cell_length_b                   9.0192(6)
_cell_length_c                   26.8007(17)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1516.68(17)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4142
_cell_measurement_theta_min      2.38
_cell_measurement_theta_max      26.05
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             648
_exptl_absorpt_coefficient_mu    0.270
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9211
_exptl_absorpt_correction_T_max  0.9735
_exptl_absorpt_process_details   '(SADABS; Sheldrick, 1996)'

_exptl_special_details           
; 
 ? 
;
_diffrn_radiation_probe          ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEXII CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8060
_diffrn_reflns_av_R_equivalents  0.0337
_diffrn_reflns_av_sigmaI/netI    0.0376
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.38
_diffrn_reflns_theta_max         25.35
_reflns_number_total             2773
_reflns_number_gt                2439
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0409P)²+0.0644P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.02(6)
_refine_ls_number_reflns         2773
_refine_ls_number_parameters     186
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0324
_refine_ls_wR_factor_ref         0.0777
_refine_ls_wR_factor_gt          0.0742
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_restrained_S_all      1.027
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cl1 Cl 0.47908(8) 0.47433(6) 0.964040(18) 0.02813(14) Uani 1 1 d . . .
O1 O -0.0972(3) 0.4094(2) 0.71956(6) 0.0510(5) Uani 1 1 d . . .
O2 O -0.3779(3) 0.52601(18) 0.77900(6) 0.0383(4) Uani 1 1 d . . .
O3 O 0.4781(3) -0.08977(18) 0.90958(6) 0.0402(4) Uani 1 1 d . . .
H3 H 0.5913 -0.1199 0.9211 0.060 Uiso 1 1 calc R . .
O4 O 0.5141(2) 0.08499(16) 0.96786(5) 0.0304(3) Uani 1 1 d . . .
O5 O 0.3518(3) 0.65042(16) 1.05675(5) 0.0311(4) Uani 1 1 d . . .
H5A H 0.3665 0.6034 1.0308 0.047 Uiso 1 1 calc R . .
N1 N 0.1470(3) 0.21984(19) 0.94404(6) 0.0225(4) Uani 1 1 d . . .
H1A H 0.2473 0.2908 0.9464 0.027 Uiso 1 1 calc R . .
H1B H 0.1264 0.1819 0.9747 0.027 Uiso 1 1 calc R . .
C1 C -0.0557(3) 0.2878(3) 0.92615(7) 0.0255(5) Uani 1 1 d . . .
H1C H -0.0800 0.3797 0.9441 0.031 Uiso 1 1 calc R . .
H1D H -0.1729 0.2213 0.9337 0.031 Uiso 1 1 calc R . .
C2 C -0.0542(3) 0.3193(2) 0.87084(7) 0.0221(5) Uani 1 1 d . . .
C3 C 0.0970(3) 0.2589(2) 0.83953(7) 0.0234(5) Uani 1 1 d . . .
C4 C 0.2771(3) 0.1653(2) 0.85906(7) 0.0245(5) Uani 1 1 d . . .
H4A H 0.4050 0.2253 0.8614 0.029 Uiso 1 1 calc R . .
H4B H 0.3050 0.0851 0.8358 0.029 Uiso 1 1 calc R . .
C5 C 0.2252(3) 0.1006(2) 0.91038(7) 0.0213(5) Uani 1 1 d . . .
H5 H 0.1143 0.0248 0.9068 0.026 Uiso 1 1 calc R . .
C6 C 0.4211(3) 0.0315(2) 0.93294(7) 0.0239(5) Uani 1 1 d . . .
C7 C 0.0841(4) 0.2881(2) 0.78812(7) 0.0274(5) Uani 1 1 d . . .
H7 H 0.1842 0.2468 0.7666 0.033 Uiso 1 1 calc R . .
C8 C -0.0734(4) 0.3763(2) 0.76930(7) 0.0322(6) Uani 1 1 d . . .
C9 C -0.2275(4) 0.4385(2) 0.80134(8) 0.0277(5) Uani 1 1 d . . .
C10 C 0.0690(7) 0.3584(4) 0.68769(10) 0.1024(17) Uani 1 1 d U . .
H10A H 0.2018 0.4016 0.6979 0.154 Uiso 1 1 calc R . .
H10B H 0.0386 0.3869 0.6539 0.154 Uiso 1 1 calc R . .
H10C H 0.0786 0.2523 0.6897 0.154 Uiso 1 1 calc R . .
C11 C -0.5327(4) 0.5940(3) 0.81060(10) 0.0436(6) Uani 1 1 d . . .
H11A H -0.6184 0.5187 0.8260 0.065 Uiso 1 1 calc R . .
H11B H -0.6220 0.6581 0.7911 0.065 Uiso 1 1 calc R . .
H11C H -0.4617 0.6508 0.8359 0.065 Uiso 1 1 calc R . .
C12 C -0.2160(3) 0.4097(2) 0.85148(8) 0.0242(5) Uani 1 1 d . . .
H12 H -0.3166 0.4505 0.8729 0.029 Uiso 1 1 calc R . .
C14 C 0.4687(4) 0.7861(3) 1.05353(10) 0.0429(6) Uani 1 1 d . . .
H14C H 0.6179 0.7646 1.0503 0.064 Uiso 1 1 calc R . .
H14B H 0.4452 0.8435 1.0832 0.064 Uiso 1 1 calc R . .
H14A H 0.4214 0.8412 1.0250 0.064 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cl1 0.0269(3) 0.0300(3) 0.0275(3) -0.0011(2) 0.0043(2) -0.0004(2)
O1 0.0773(14) 0.0571(11) 0.0186(8) 0.0089(8) 0.0017(8) 0.0326(11)
O2 0.0386(9) 0.0416(9) 0.0346(8) 0.0080(8) -0.0040(7) 0.0144(8)
O3 0.0445(11) 0.0366(9) 0.0394(9) -0.0115(8) -0.0172(8) 0.0155(9)
O4 0.0287(8) 0.0350(8) 0.0275(8) -0.0030(7) -0.0087(7) 0.0018(7)
O5 0.0357(9) 0.0277(9) 0.0297(8) -0.0030(7) 0.0035(8) -0.0053(7)
N1 0.0224(9) 0.0272(10) 0.0180(8) 0.0003(8) 0.0004(7) -0.0047(8)
C1 0.0230(11) 0.0327(12) 0.0207(10) -0.0007(9) 0.0017(9) 0.0026(10)
C2 0.0224(11) 0.0228(11) 0.0211(10) -0.0004(8) -0.0020(9) -0.0039(9)
C3 0.0253(11) 0.0239(11) 0.0211(10) 0.0014(9) -0.0022(9) -0.0001(9)
C4 0.0245(11) 0.0285(12) 0.0206(10) -0.0021(9) 0.0018(9) 0.0002(10)
C5 0.0226(11) 0.0204(11) 0.0210(10) -0.0013(9) -0.0010(8) -0.0044(9)
C6 0.0261(11) 0.0252(11) 0.0205(10) 0.0021(9) 0.0011(8) -0.0002(10)
C7 0.0351(13) 0.0283(12) 0.0187(10) -0.0002(9) 0.0042(9) 0.0046(10)
C8 0.0473(15) 0.0301(13) 0.0191(11) 0.0031(9) -0.0019(10) 0.0054(11)
C9 0.0326(12) 0.0237(12) 0.0266(12) 0.0028(9) -0.0031(9) 0.0037(10)
C10 0.150(4) 0.135(3) 0.0222(13) 0.0299(18) 0.0291(19) 0.106(3)
C11 0.0356(14) 0.0432(14) 0.0521(14) 0.0079(13) -0.0006(12) 0.0121(13)
C12 0.0231(11) 0.0234(11) 0.0262(11) -0.0002(9) 0.0005(9) 0.0000(10)
C14 0.0462(15) 0.0299(13) 0.0525(14) 0.0026(12) 0.0080(13) -0.0040(13)

_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C8 1.374(3) . ?
O1 C10 1.424(3) . ?
O2 C9 1.368(3) . ?
O2 C11 1.427(3) . ?
O3 C6 1.310(2) . ?
O3 H3 0.8200 . ?
O4 C6 1.204(2) . ?
O5 C14 1.429(3) . ?
O5 H5A 0.8200 . ?
N1 C5 1.487(3) . ?
N1 C1 1.491(3) . ?
N1 H1A 0.9000 . ?
N1 H1B 0.9000 . ?
C1 C2 1.509(3) . ?
C1 H1C 0.9700 . ?
C1 H1D 0.9700 . ?
C2 C3 1.379(3) . ?
C2 C12 1.402(3) . ?
C3 C7 1.405(3) . ?
C3 C4 1.505(3) . ?
C4 C5 1.529(3) . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
C5 C6 1.505(3) . ?
C5 H5 0.9800 . ?
C7 C8 1.365(3) . ?
C7 H7 0.9300 . ?
C8 C9 1.410(3) . ?
C9 C12 1.371(3) . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 H12 0.9300 . ?
C14 H14C 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14A 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C8 O1 C10 115.6(2) . . ?
C9 O2 C11 117.23(18) . . ?
C6 O3 H3 109.5 . . ?
C14 O5 H5A 109.5 . . ?
C5 N1 C1 112.54(15) . . ?
C5 N1 H1A 109.1 . . ?
C1 N1 H1A 109.1 . . ?
C5 N1 H1B 109.1 . . ?
C1 N1 H1B 109.1 . . ?
H1A N1 H1B 107.8 . . ?
N1 C1 C2 112.81(16) . . ?
N1 C1 H1C 109.0 . . ?
C2 C1 H1C 109.0 . . ?
N1 C1 H1D 109.0 . . ?
C2 C1 H1D 109.0 . . ?
H1C C1 H1D 107.8 . . ?
C3 C2 C12 120.18(18) . . ?
C3 C2 C1 121.87(18) . . ?
C12 C2 C1 117.93(18) . . ?
C2 C3 C7 118.90(19) . . ?
C2 C3 C4 121.77(17) . . ?
C7 C3 C4 119.31(18) . . ?
C3 C4 C5 111.53(17) . . ?
C3 C4 H4A 109.3 . . ?
C5 C4 H4A 109.3 . . ?
C3 C4 H4B 109.3 . . ?
C5 C4 H4B 109.3 . . ?
H4A C4 H4B 108.0 . . ?
N1 C5 C6 108.97(15) . . ?
N1 C5 C4 109.87(17) . . ?
C6 C5 C4 110.19(17) . . ?
N1 C5 H5 109.3 . . ?
C6 C5 H5 109.3 . . ?
C4 C5 H5 109.3 . . ?
O4 C6 O3 125.0(2) . . ?
O4 C6 C5 122.83(19) . . ?
O3 C6 C5 112.13(17) . . ?
C8 C7 C3 120.87(19) . . ?
C8 C7 H7 119.6 . . ?
C3 C7 H7 119.6 . . ?
C7 C8 O1 124.3(2) . . ?
C7 C8 C9 120.22(19) . . ?
O1 C8 C9 115.5(2) . . ?
O2 C9 C12 125.1(2) . . ?
O2 C9 C8 115.86(18) . . ?
C12 C9 C8 119.0(2) . . ?
O1 C10 H10A 109.5 . . ?
O1 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
O1 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
O2 C11 H11A 109.5 . . ?
O2 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
O2 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C9 C12 C2 120.8(2) . . ?
C9 C12 H12 119.6 . . ?
C2 C12 H12 119.6 . . ?
O5 C14 H14C 109.5 . . ?
O5 C14 H14B 109.5 . . ?
H14C C14 H14B 109.5 . . ?
O5 C14 H14A 109.5 . . ?
H14C C14 H14A 109.5 . . ?
H14B C14 H14A 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C5 N1 C1 C2 -44.2(2) . . . . ?
N1 C1 C2 C3 14.4(3) . . . . ?
N1 C1 C2 C12 -167.25(18) . . . . ?
C12 C2 C3 C7 -0.8(3) . . . . ?
C1 C2 C3 C7 177.5(2) . . . . ?
C12 C2 C3 C4 178.05(19) . . . . ?
C1 C2 C3 C4 -3.7(3) . . . . ?
C2 C3 C4 C5 21.3(3) . . . . ?
C7 C3 C4 C5 -159.83(19) . . . . ?
C1 N1 C5 C6 -176.18(16) . . . . ?
C1 N1 C5 C4 63.0(2) . . . . ?
C3 C4 C5 N1 -49.6(2) . . . . ?
C3 C4 C5 C6 -169.67(17) . . . . ?
N1 C5 C6 O4 -11.7(3) . . . . ?
C4 C5 C6 O4 108.9(2) . . . . ?
N1 C5 C6 O3 169.53(17) . . . . ?
C4 C5 C6 O3 -69.9(2) . . . . ?
C2 C3 C7 C8 0.9(3) . . . . ?
C4 C3 C7 C8 -178.0(2) . . . . ?
C3 C7 C8 O1 -179.7(2) . . . . ?
C3 C7 C8 C9 -0.7(3) . . . . ?
C10 O1 C8 C7 -6.6(4) . . . . ?
C10 O1 C8 C9 174.4(3) . . . . ?
C11 O2 C9 C12 0.9(3) . . . . ?
C11 O2 C9 C8 -178.3(2) . . . . ?
C7 C8 C9 O2 179.6(2) . . . . ?
O1 C8 C9 O2 -1.3(3) . . . . ?
C7 C8 C9 C12 0.3(3) . . . . ?
O1 C8 C9 C12 179.4(2) . . . . ?
O2 C9 C12 C2 -179.4(2) . . . . ?
C8 C9 C12 C2 -0.3(3) . . . . ?
C3 C2 C12 C9 0.5(3) . . . . ?
C1 C2 C12 C9 -177.8(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1A Cl1 0.90 2.25 3.1459(18) 171.4 .
N1 H1B Cl1 0.90 2.35 3.2010(17) 157.2 4_457
O3 H3 O5 0.82 1.76 2.571(2) 169.1 4_557
O5 H5A Cl1 0.82 2.25 3.0552(16) 168.0 .

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.35
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.145
_refine_diff_density_rms         0.038
_database_code_depnum_ccdc_archive 'CCDC 843101'
